Ultrafast Solvation Dynamics of an Ion in the gamma-Cyclodextrin Cavity: The Role of Restricted Environment

A detailed study of the solvation dynamics of a charged coumarin dye molecule in gamma-cyclodextrin/water has been carried out by using two different theoretical approaches. The first approach is based on a multishell continuum model (MSCM). This model predicts the time scales of the dynamics rather well, provided an accurate description of the frequency-dependent dielectric function is supplied. The reason for this rather surprising agreement is 2-fold. First, there is a cancellation of errors, second, the two-zone model mimics the heterogeneous microenvironment surrounding the ion rather well. The second approach is based on the molecular hydrodynamics theory (MI-IT). In this molecular approach, the solvation dynamics has been studied by restricting the translational motion of the solvent molecules enclosed within the cavity. The results from the molecular theory are also in good agreement with the experimental results. Our study indicates that, in the present case, the restricted environment affects only the long time decay of the solvation time correlation function. The short time dynamics is still governed by the librational (and/or vibrational) modes present in bulk water.

Dynamics of dense sheared granular flows. Part II. The relative velocity distributions

The distribution of relative velocities between colliding particles in shear flows of inelastic spheres is analysed in the Volume fraction range 0.4-0.64. Particle interactions are considered to be due to instantaneous binary collisions, and the collision model has a normal coefficient of restitution e(n) (negative of the ratio of the post- and pre-collisional relative velocities of the particles along the line joining the centres) and a tangential coefficient of restitution e(t) (negative of the ratio of post- and pre-collisional velocities perpendicular to line joining the centres). The distribution or pre-collisional normal relative velocities (along the line Joining the centres of the particles) is Found to be an exponential distribution for particles with low normal coefficient of restitution in the range 0.6-0.7. This is in contrast to the Gaussian distribution for the normal relative velocity in all elastic fluid in the absence of shear. A composite distribution function, which consists of an exponential and a Gaussian component, is proposed to span the range of inelasticities considered here. In the case of roughd particles, the relative velocity tangential to the surfaces at contact is also evaluated, and it is found to be close to a Gaussian distribution even for highly inelastic particles.Empirical relations are formulated for the relative velocity distribution. These are used to calculate the collisional contributions to the pressure, shear stress and the energy dissipation rate in a shear flow. The results of the calculation were round to be in quantitative agreement with simulation results, even for low coefficients of restitution for which the predictions obtained using the Enskog approximation are in error by an order of magnitude. The results are also applied to the flow down an inclined plane, to predict the angle of repose and the variation of the volume fraction with angle of inclination. These results are also found to be in quantitative agreement with previous simulations.

Buckling, stiffening, and negative dissipation in the dynamics of a biopolymer in an active medium

We present a generic theory for the dynamics of a stiff filament under tension, in an active medium with orientational correlations, such as a microtubule in contractile actin. In sharp contrast to the case of a passive medium, we find the filament can stiffen, and possibly oscillate or buckle, depending on both the contractile or tensile nature of the activity and the filament-medium anchoring interaction. We also demonstrate a strong violation of the fluctuation-dissipation (FD) relation in the effective dynamics of the filament, including a negative FD ratio. Our approach is also of relevance to the dynamics of axons, and our model equations bear a remarkable formal similarity to those in recent work [Martin P, Hudspeth AJ, Juelicher F (2001) Proc Natl Acad Sci USA 98: 14380-14385] on auditory hair cells. Detailed tests of our predictions can be made by using a single filament in actomyosin extracts or bacterial suspensions.

Dynamics of Barrierless and Activated Chemical Reactions in a Dispersive Medium within the Fractional Diffusion Equation Approach

Barrierless chemical reactions have often been modeled as a Brownian motion on a one-dimensional harmonic potential energy surface with a position-dependent reaction sink or window located near the minimum of the surface. This simple (but highly successful) description leads to a nonexponential survival probability only at small to intermediate times but exponential decay in the long-time limit. However, in several reactive events involving proteins and glasses, the reactions are found to exhibit a strongly nonexponential (power law) decay kinetics even in the long time. In order to address such reactions, here, we introduce a model of barrierless chemical reaction where the motion along the reaction coordinate sustains dispersive diffusion. A complete analytical solution of the model can be obtained only in the frequency domain, but an asymptotic solution is obtained in the limit of long time. In this case, the asymptotic long-time decay of the survival probability is a power law of the Mittag−Leffler functional form. When the barrier height is increased, the decay of the survival probability still remains nonexponential, in contrast to the ordinary Brownian motion case where the rate is given by the Smoluchowski limit of the well-known Kramers' expression. Interestingly, the reaction under dispersive diffusion is shown to exhibit strong dependence on the initial state of the system, thus predicting a strong dependence on the excitation wavelength for photoisomerization reactions in a dispersive medium. The theory also predicts a fractional viscosity dependence of the rate, which is often observed in the reactions occurring in complex environments.

Deformation dynamics of SS-316 Between 1023-K TO 1223-K In The Framework of Cottrell-Stokes Law

Kocks' formalism for analysing steady state deformation data for the case where Cottrell-Stokes law is valid is extended to incorporate possible back stresses from solution and/or precipitation hardening, and dependence of pre-exponential factor on the applied stress. A simple graphical procedure for exploiting these equations is demonstrated by analyzing tensile steady state data for a type 316 austentic stainless steel for the temperature range 1023 to 1223 K. In this instance, the computed back stress values turned out to be negative, a physically meaningless result. This shows that for SS 316, deformation in this temperature regime can not be interpreted in terms of a mechanism that obeys Cottrell-Stokes law.

The Case for Non-Cooperative Multihoming of Users to Access Points in IEEE 802.11 WLANs

In many cases, a mobile user has the option of connecting to one of several IEEE 802.11 access points (APs),each using an independent channel. User throughput in each AP is determined by the number of other users as well as the frame size and physical rate being used. We consider the scenario where users could multihome, i.e., split their traffic amongst all the available APs, based on the throughput they obtain and the price charged. Thus, they are involved in a non-cooperative game with each other. We convert the problem into a fluid model and show that under a pricing scheme, which we call the cost price mechanism, the total system throughput is maximized,i.e., the system suffers no loss of efficiency due to selfish dynamics. We also study the case where the Internet Service Provider (ISP) could charge prices greater than that of the cost price mechanism. We show that even in this case multihoming outperforms unihoming, both in terms of throughput as well as profit to the ISP.

A unified model for the dynamics of driven ribbon with strain and magnetic order parameters

We develop a unified model to explain the dynamics of driven one dimensional ribbon for materials with strain and magnetic order parameters. We show that the model equations in their most general form explain several results on driven magnetostrictive metallic glass ribbons such as the period doubling route to chaos as a function of a dc magnetic field in the presence of a sinusoidal field, the quasiperiodic route to chaos as a function of the sinusoidal field for a fixed dc field, and induced and suppressed chaos in the presence of an additional low amplitude near resonant sinusoidal field. We also investigate the influence of a low amplitude near resonant field on the period doubling route. The model equations also exhibit symmetry restoring crisis with an exponent close to unity. The model can be adopted to explain certain results on magnetoelastic beam and martensitic ribbon under sinusoidal driving conditions. In the latter case, we find interesting dynamics of a periodic one orbit switching between two equivalent wells as a function of an ac magnetic field that eventually makes a direct transition to chaos under resonant driving condition. The model is also applicable to magnetomartensites and materials with two order parameters. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4790845]

Dynamics of a flexible splitter plate in the wake of a circular cylinder

Rigid splitter plates in the wake of bluff bodies are known to suppress the primary vortex shedding. In the present work, we experimentally study the problem of a flexible splitter plate in the wake of a circular cylinder. In this case, the splitter plate is free to continuously deform along its length due to the fluid forces acting on it; the flexural rigidity (EI) of the plate being an important parameter. Direct visualizations of the splitter plate motions, for very low values of flexural rigidity (EI), indicate periodic traveling wave type deformations of the splitter plate with maximum tip amplitudes of the order of I cylinder diameter. As the Reynolds number based on cylinder diameter is varied, two regimes of periodic splitter plate motions are found that are referred to as mode I and mode II, with a regime of aperiodic motions between them. The frequency of plate motions in both periodic modes is found to be close to the plane cylinder Strouhal number of about 0.2, while the average frequencies in the non-periodic regime are substantially lower. The measured normalized phase speed of the traveling wave for both periodic modes is also close to the convection speed of vortices in the plane cylinder wake. As the flexural rigidity of the plate (EI) is increased, the response of the plate was found to shift to the right when plotted with flow speed or Re. To better capture the effect of varying EI, we define and use a non-dimensional bending stiffness, K*, similar to the ones used in the flag flutter problem, K*=EI/(0.5 rho(UL3)-L-2), where U is the free-stream velocity and L is the splitter plate length. Amplitude data for different EI cases when plotted against this parameter appear to collapse on to a single curve for a given splitter plate length. Measurements of the splitter plate motions for varying splitter plate lengths indicate that plates that are substantially larger than the formation length of the plane cylinder wake have similar responses, while shorter plates show significant differences.

Hierarchical sampling for metastable conformers determines biomolecular recognition: the case of malectin and diglucosylated N-glycan interactions

Structural information over the entire course of binding interactions based on the analyses of energy landscapes is described, which provides a framework to understand the events involved during biomolecular recognition. Conformational dynamics of malectin's exquisite selectivity for diglucosylated N-glycan (Dig-N-glycan), a highly flexible oligosaccharide comprising of numerous dihedral torsion angles, are described as an example. For this purpose, a novel approach based on hierarchical sampling for acquiring metastable molecular conformations constituting low-energy minima for understanding the structural features involved in a biologic recognition is proposed. For this purpose, four variants of principal component analysis were employed recursively in both Cartesian space and dihedral angles space that are characterized by free energy landscapes to select the most stable conformational substates. Subsequently, k-means clustering algorithm was implemented for geometric separation of the major native state to acquire a final ensemble of metastable conformers. A comparison of malectin complexes was then performed to characterize their conformational properties. Analyses of stereochemical metrics and other concerted binding events revealed surface complementarity, cooperative and bidentate hydrogen bonds, water-mediated hydrogen bonds, carbohydrate-aromatic interactions including CH-pi and stacking interactions involved in this recognition. Additionally, a striking structural transition from loop to beta-strands in malectin CRD upon specific binding to Dig-N-glycan is observed. The interplay of the above-mentioned binding events in malectin and Dig-N-glycan supports an extended conformational selection model as the underlying binding mechanism.

Dynamics of the chemical bond: inter- and intra-molecular hydrogen bond

In this discussion, we show that a static definition of a `bond' is not viable by looking at a few examples for both inter-and intra-molecular hydrogen bonding. This follows from our earlier work (Goswami and Arunan, Phys. Chem. Chem. Phys. 2009, 11, 8974) which showed a practical way to differentiate `hydrogen bonding' from `van der Waals interaction'. We report results from ab initio and atoms in molecules theoretical calculations for a series of Rg center dot center dot center dot HX complexes (Rg = He/Ne/Ar and X = F/Cl/Br) and ethane-1,2-diol. Results for the Rg center dot center dot center dot HX/DX complexes show that Rg center dot center dot center dot DX could have a `deuterium bond' even when Rg center dot center dot center dot HX is not `hydrogen bonded', according to the practical criterion given by Goswami and Arunan. Results for ethane-1,2-diol show that an `intra-molecular hydrogen bond' can appear during a normal mode vibration which is dominated by the O center dot center dot center dot O stretching, though a `bond' is not found in the equilibrium structure. This dynamical `bond' formation may nevertheless be important in ensuring the continuity of electron density across a molecule. In the former case, a vibration `breaks' an existing bond and in the later case, a vibration leads to `bond' formation. In both cases, the molecule/complex stays bound irrespective of what happens to this `hydrogen bond'. Both these cases push the borders on the recent IUPAC recommendation on hydrogen bonding (Arunan et al. Pure. Appl. Chem. 2011, 83 1637) and justify the inclusive nature of the definition.

Dynamics of a dilute sheared inelastic fluid. II. The effect of correlations

The effect of correlations on the viscosity of a dilute sheared inelastic fluid is analyzed using the ring-kinetic equation for the two-particle correlation function. The leading-order contribution to the stress in an expansion in epsilon=(1-e)(1/2) is calculated, and it is shown that the leading-order viscosity is identical to that obtained from the Green-Kubo formula, provided the stress autocorrelation function in a sheared steady state is used in the Green-Kubo formula. A systemmatic extension of this to higher orders is also formulated, and the higher-order contributions to the stress from the ring-kinetic equation are determined in terms of the terms in the Chapman-Enskog solution for the Boltzmann equation. The series is resummed analytically to obtain a renormalized stress equation. The most dominant contributions to the two-particle correlation function are products of the eigenvectors of the conserved hydrodynamic modes of the two correlated particles. In Part I, it was shown that the long-time tails of the velocity autocorrelation function are not present in a sheared fluid. Using those results, we show that correlations do not cause a divergence in the transport coefficients; the viscosity is not divergent in two dimensions, and the Burnett coefficients are not divergent in three dimensions. The equations for three-particle and higher correlations are analyzed diagrammatically. It is found that the contributions due to the three-particle and higher correlation functions to the renormalized viscosity are smaller than those due to the two-particle distribution function in the limit epsilon -> 0. This implies that the most dominant correlation effects are due to the two-particle correlations.

The dynamics of polymerized carbon nanotubes in semiconductor polymer electronics and electro-mechanical sensing

Polymerized carbon nanotubes (CNTs) are promising materials for polymer-based electronics and electro-mechanical sensors. The advantage of having a polymer nanolayer on CNTs widens the scope for functionalizing it in various ways for polymer electronic devices. However, in this paper, we show for the first time experimentally that, due to a resistive polymer layer having carbon nanoparticle inclusions and polymerized carbon nanotubes, an interesting dynamics can be exploited. We first show analytically that the relative change in the resistance of a single isolated semiconductive nanotube is directly proportional to the axial and torsional dynamic strains, when the strains are small, whereas, in polymerized CNTs, the viscoelasticity of the polymer and its effective electrical polarization give rise to nonlinear effects as a function of frequency and bias voltage. A simplified formula is derived to account for these effects and validated in the light of experimental results. CNT–polymer-based channels have been fabricated on a PZT substrate. Strain sensing performance of such a one-dimensional channel structure is reported. For a single frequency modulated sine pulse as input, which is common in elastic and acoustic wave-based diagnostics, imaging, microwave devices, energy harvesting, etc, the performance of the fabricated channel has been found to be promising.

Programming an FPGA to Emulate the Dynamics of DC Machines

This paper presents the programming an FPGA (Field Programmable Gate Array) to emulate the dynamics of DC machines. FPGA allows high speed real time simulation with high precision. The described design includes block diagram representation of DC machine, which contain all arithmetic and logical operations. The real time simulation of the machine in FPGA is controlled by user interfaces they are Keypad interface, LCD display on-line and digital to analog converter. This approach provides emulation of electrical machine by changing the parameters. Separately Exited DC machine implemented and experimental results are presented.

Dynamics of the ammonium ion in the ferroelectric transition in sodium ammonium selenate, NaNH4SeO4·2H2O-an E.S.R. study

E.S.R. investigations of γ-irradiated ferroelectric Sodium ammonium selenate, NaNH4SeO4•2H2O and its deuteriated analogue in powder and single crystal forms have led to a deeper understanding of the nature of the ferroelectric transition of 180 K. A number of paramagnetic species formed due to γ-irradiation have been identified on the basis of their g-factors and hyperfine features from 77Se. The radical SeO4 has been used as a microprobe in studying the phase transition.

Classical Langevin dynamics of a charged particle moving on a sphere and diamagnetism: A surprise

It is generally known that the orbital diamagnetism of a classical system of charged particles in thermal equilibrium is identically zero —the Bohr-van Leeuwen theorem. Physically, this null result derives from the exact cancellation of the orbital diamagnetic moment associated with the complete cyclotron orbits of the charged particles by the paramagnetic moment subtended by the incomplete orbits skipping the boundary in the opposite sense. Motivated by this crucial but subtle role of the boundary, we have simulated here the case of a finite but unbounded system, namely that of a charged particle moving on the surface of a sphere in the presence of an externally applied uniform magnetic field. Following a real space-time approach based on the classical Langevin equation, we have computed the orbital magnetic moment that now indeed turns out to be non-zero and has the diamagnetic sign. To the best of our knowledge, this is the first report of the possibility of finite classical diamagnetism in principle, and it is due to the avoided cancellation.